CN104685083A - Ag-Pd-Cu-Co alloy for uses in electrical/electronic devices - Google Patents

Ag-Pd-Cu-Co alloy for uses in electrical/electronic devices Download PDF

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Publication number
CN104685083A
CN104685083A CN201280076045.6A CN201280076045A CN104685083A CN 104685083 A CN104685083 A CN 104685083A CN 201280076045 A CN201280076045 A CN 201280076045A CN 104685083 A CN104685083 A CN 104685083A
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CN
China
Prior art keywords
solder
alloy
quality
wettability
metallic substance
Prior art date
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Pending
Application number
CN201280076045.6A
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Chinese (zh)
Inventor
汲田英生
宍野龙
闰景树
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Tokuriki Honten Co Ltd
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Tokuriki Honten Co Ltd
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Publication of CN104685083A publication Critical patent/CN104685083A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/06—Alloys containing less than 50% by weight of each constituent containing zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/04—Alloys containing less than 50% by weight of each constituent containing tin or lead
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C22C5/08—Alloys based on silver with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/14—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of noble metals or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
    • G01R1/02—General constructional details
    • G01R1/06—Measuring leads; Measuring probes
    • G01R1/067—Measuring probes
    • G01R1/06711—Probe needles; Cantilever beams; "Bump" contacts; Replaceable probe pins
    • G01R1/06733—Geometry aspects
    • G01R1/06738—Geometry aspects related to tip portion
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
    • G01R1/02—General constructional details
    • G01R1/06—Measuring leads; Measuring probes
    • G01R1/067—Measuring probes
    • G01R1/06711—Probe needles; Cantilever beams; "Bump" contacts; Replaceable probe pins
    • G01R1/06755—Material aspects
    • G01R1/06761—Material aspects related to layers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The present invention provides a metal material for uses in electrical/electronic devices, which is characterized by being formed of 20-50% by mass of Ag, 20-50% by mass of Pd, 10-40% by mass of Cu and 0.5-30% by mass of Co, and which is also characterized by having low contact resistance, excellent oxidation resistance, high hardness, excellent processability, low wettability with respect to Sn alloy solders, and resistance to Sn alloy solder erosion.

Description

The Ag-Pd-Cu-Co alloy of elec-tric-electronic equipment purposes
Technical field
The present invention relates to a kind of metallic substance of elec-tric-electronic equipment purposes.
Background technology
Metallic substance for elec-tric-electronic equipment purposes requires many characteristics such as low contact resistance and excellent scale resistance, and therefore, the expensive precious metal alloys such as Pt alloy, Au alloy, Pd alloy, Ag alloy are widely used.But, according to the difference of use (for detecting the probe etc. of semiconductor integrated circuit etc.), except low contact resistance and scale resistance, also need hardness (wear resistance) etc.Therefore, show the Pt alloy of high rigidity under being preferably used in the state implementing plastic working, the Au alloy, Pd alloy etc. (such as patent documentation 1, patent documentation 2) of Ir alloy etc. or precipitation hardening.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 4176133 publication
Patent documentation 2: Japanese Patent No. 4216823 publication
Patent documentation 3: the probe of No. 2007/034921st, International Publication particularly just for detecting semiconductor integrated circuit etc. (, is denoted as probe below.), according to the difference of detected object, adopt all kinds (shape) such as cantilever, Naja (cobra), spring, according to the type of each probe, required characteristic is also different separately.
Summary of the invention
Invent problem to be solved
When the detected object of popping one's head in is Sn alloy solder bump (bump) etc., if the material of probe is for the Sn comprised in Sn solder, resistance to fouling is low and wettability is excellent, when then carrying out tens thousand of repetitive operations test, Sn solder is easily attached to probe, its result, makes resistance value change, and therefore can not test exactly sometimes.
Therefore, as the countermeasure of reply Sn solder to probe attachment, after the test carrying out certain number of times, the front end of cleaning probe.But, if Sn solder can be made not easily to be attached to probe, then can not only reduce wash number, and can test more accurately, detect percent of pass and also improve.
In the face of such demand, research, the exploitation of implementing plating Ag, plating Pd etc. are carried out.But, owing to carrying out tens thousand of repetitive operations test and cleaning, so the misgivings such as coating wearing and tearing can be there are.In addition, also consider the microminiaturization along with detected object in recent years, self the microminiaturization of popping one's head in, also in development, may be difficult to carry out plating (such as patent documentation 3) sometimes.
For solving the method for problem
The invention provides a kind of Ag-Pd-Cu-Co alloy of elec-tric-electronic equipment purposes, it is characterized in that, this Ag-Pd-Cu-Co alloy passes through the element-specific Co adding 0.5 ~ 30 quality % in the Ag-Pd-Cu alloy of the Ag, the Pd of 20 ~ 50 quality % that comprise 20 ~ 50 quality %, the Cu of 10 ~ 40 quality %, thus using the Sn that comprises in Sn solder as main object, wettability is low, and has resistance to fouling.It should be noted that, the Pb-free solder that it is representative that the Sn solder in the present invention refers to Sn-Cu system, Sn-Ag system, Sn-Ag-Cu system, Sn-Zn-Bi system, Sn-Ag-In system, Sn-Zn-Al system etc.
In the present invention, why the addition of Co is set as the reason of 0.5 ~ 30 quality %, because the wettability for Sn solder is low, and resistance to fouling is improved, when the addition of Co is lower than 0.5 quality %, the effect that the resistance to fouling of Sn solder and wettability are reduced can not be shown, if the addition of Co is more than 30 quality %, then processibility obviously reduces, and can not obtain the hardness of regulation.
In addition, feature of the present invention is also, to with the addition of in the alloy of Co in Ag-Pd-Cu alloy of the present invention, as the Addition ofelements improving characteristic according to purposes, add the Addition ofelements of more than at least one being selected from Ni, Pt, Re, Rh, Ru, Si, Sn, Zn, B, In, Nb, Ta of the Au of 0.1 ~ 10 quality % and/or 0.1 ~ 3.0 quality % further.The reason of adding the Au of 0.1 ~ 10 quality % is to improve oxidation-resistance and hardness, and when the addition of Au is lower than 0.1 quality %, without this effect, if more than 10 quality %, then processibility is deteriorated.The Addition ofelements adding more than at least one being selected from Ni, Pt, Re, Rh, Ru, Si, Sn, Zn, B, In, Nb, Ta of 0.1 ~ 3.0 quality % is to improve hardness.Ni also can be used as the Addition ofelements of the curved characteristic after improving Ag-Pd-Cu alloy deposition.Re, Rh and Ru also can as the Addition ofelements making crystal grain miniaturization.
The effect of invention
According to the present invention, can provide a kind of metallic substance of elec-tric-electronic equipment purposes, it is characterized in that, the low and excellent in oxidation resistance of contact resistance, hardness is high, excellent in workability, and the wettability for Sn solder is low, and has anti-Sn solder aggressiveness.
Embodiment
Below embodiments of the invention are described.Make alloy pig (thickness 10mm × width 10mm × length 100mm) by vacuum melting, this alloy pig adds Co or adds the Addition ofelements improving characteristic according to purposes in each Ag-Pd-Cu alloy to be made.
After the removing shrinkage cavity fusion defects part such as (Soup draws け), be repeatedly rolled processing and solution treatment (800 DEG C × 1hr, H 2and N 2mixed atmosphere in), until thickness of slab is 0.3mm, it is about 75% that rolling is machined to finished section minification, it can be used as test film (thickness 0.3mm × width 20mm × length 20mm), at H 2and N 2mixed atmosphere under the condition of 300 ~ 500 DEG C × 1hr, carry out precipitation hardening.In addition, the measurement of hardness of test film utilizes Vickers pyramid hardness testing machine, measures its surface hardness with HV0.2.
With regard to the height of the wettability for Sn solder and the rodent investigation of anti-Sn solder, the Sn solder of thickness setting 0.8mm × width 1.0mm × length 10mm on test film, heat at 275 DEG C and keep 1min, then the Sn solder of melting is cooled, afterwards by the outward appearance of viewing test sheet, evaluate the height of the wettability for Sn solder.The judgement criteria of wettability height is as follows: be A by the width of melting Sn solder lower than the average evaluation that width is 3.0mm, and being that the average evaluation of 3.0mm ~ 4.9mm is B by width, is that the average evaluation of more than 5.0mm is C by width.In addition, by the fractography of viewing test sheet and Sn solder, anti-Sn solder aggressiveness is evaluated.The rodent judgement criteria of anti-Sn solder is as follows: by Sn to the depth of erosion of test film lower than 30 μm be evaluated as A, by Sn to the depth of erosion of test film be 30 ~ 59 μm be evaluated as B, by Sn to the depth of erosion of test film be more than 60 μm be evaluated as C.
The melting method of the present embodiment uses vacuum melting, but also can use the various melting of metal methods beyond vacuum melting, such as, can apply the various melting of metal method such as continuous metal cast process, gas fusing.In addition, infer and also can be melted by the novel melting method may established from now on.
Because the present embodiment manufactures sheet material as test film, the rolling therefore implemented as one of plastic processing method process, also can shape as requested, the various plastic processing methods beyond enforcement rolling.Such as, if the shape required is wire, be then applicable to plastic working such as bracing wire processing (drawing processing) or swaged forging processing etc., these working methods suitably can be used in the probe metallic substance etc. manufacturing and pop one's head in and use.In addition, infer and also can be processed by the NEW PLASTIC working method may established from now on.
The Ecosolder (registered trademark) (Sn-Ag-Cu system) that the Sn solder used in the present embodiment manufactures for Senju Metal Industry Co., Ltd, but in other Pb-free solders (Sn solder), also confirm wettability low, anti-Sn solder aggressiveness and improve.
Hardness after representing the composition table look-up of embodiment, the height of wettability, anti-Sn solder aggressiveness, processing in table 1 and table 2 and after precipitation hardening.
By table 2 results verification to, in the comparative example 1 not adding Co in Ag-Pd-Cu and comparative example 2, height and the evaluation of anti-Sn solder aggressiveness of wettability are B, in the embodiment 1 that with the addition of the Co of 10 quality % in comparative example 1 and comparative example 2 and embodiment 2, height and the anti-Sn solder aggressiveness of wettability all improve, and are evaluated as A.
Similarly, about comparative example 3 ~ 6, the height of wettability and anti-Sn solder rodent any one be not all evaluated as the situation of A.In the alloy of embodiment 3 ~ 32, this alloy in Ag-Pd-Cu alloy, adds Co and adds the alloy being selected from least one in Au, Ni, Pt, Re, Rh, Ru, Si, Sn, Zn, B, In, Nb, Ta and obtaining further, the height of wettability now and anti-Sn solder rodent at least one be evaluated as A, and do not confirm evaluation C, the wettability confirmed for Sn solder is low, and anti-Sn solder aggressiveness improves.
Table 1
Table 2

Claims (5)

1. a metallic substance for elec-tric-electronic equipment purposes, is characterized in that:
This metallic substance by comprising Ag, the Pd of 20 ~ 50 quality % of 20 ~ 50 quality %, the alloy of the Co of the Cu of 10 ~ 40 quality % and 0.5 ~ 30 quality % forms, the wettability for Sn solder is low, has anti-Sn solder aggressiveness.
2. metallic substance as claimed in claim 1, is characterized in that:
Also comprise the Au of 0.1 ~ 10 quality %.
3., as metallic substance according to claim 1 or claim 2, it is characterized in that:
Addition ofelements also containing 0.1 ~ 3.0 quality %, described Addition ofelements is be selected from more than at least one in Ni, Pt, Re, Rh, Ru, Si, Sn, Zn, B, In, Nb, Ta.
4., as metallic substance according to claim 1 or claim 2, it is characterized in that:
Hardness during precipitation hardening after plastic working is set as 200 ~ 450HV.
5. metallic substance as claimed in claim 3, is characterized in that:
Hardness during precipitation hardening after plastic working is set as 200 ~ 450HV.
CN201280076045.6A 2012-09-28 2012-09-28 Ag-Pd-Cu-Co alloy for uses in electrical/electronic devices Pending CN104685083A (en)

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Application Number Priority Date Filing Date Title
PCT/JP2012/075253 WO2014049874A1 (en) 2012-09-28 2012-09-28 Ag-Pd-Cu-Co ALLOY FOR USES IN ELECTRICAL/ELECTRONIC DEVICES

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US (1) US20150197834A1 (en)
JP (1) JP6142347B2 (en)
KR (1) KR20150056556A (en)
CN (1) CN104685083A (en)
TW (1) TWI600773B (en)
WO (1) WO2014049874A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107075667A (en) * 2014-11-07 2017-08-18 住友金属矿山株式会社 Copper alloy target
CN110317969A (en) * 2018-03-28 2019-10-11 住友金属矿山株式会社 The overlay film of solder bonding electrodes and solder bonding electrodes, which is formed, uses copper alloy target

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JP6728057B2 (en) * 2015-03-31 2020-07-22 日本発條株式会社 Alloy materials, contact probes and connection terminals
TWI567207B (en) * 2015-03-31 2017-01-21 日本發條股份有限公司 Alloy materials, contact probe and connecting terminal
CN111411252A (en) * 2016-01-25 2020-07-14 田中贵金属工业株式会社 Sliding contact material and method for producing same
US10385424B2 (en) 2016-01-29 2019-08-20 Deringer-Ney, Inc. Palladium-based alloys
JP6647075B2 (en) * 2016-02-19 2020-02-14 日本発條株式会社 Alloy materials, contact probes and connection terminals
CN111511939B (en) * 2017-12-27 2021-09-14 株式会社德力本店 Precipitation hardening type Ag-Pd-Cu-In-B alloy
EP3960890A1 (en) * 2020-09-01 2022-03-02 Heraeus Deutschland GmbH & Co. KG Palladium copper silver ruthenium alloy
CN117015625A (en) * 2021-03-26 2023-11-07 石福金属兴业株式会社 Alloy material for probe
TW202244282A (en) * 2021-03-26 2022-11-16 日商石福金屬興業股份有限公司 Alloy material for probe pins
WO2022202658A1 (en) * 2021-03-26 2022-09-29 株式会社ヨコオ Probe
JP7072126B1 (en) 2022-02-10 2022-05-19 田中貴金属工業株式会社 Material for probe pins made of Ag-Pd-Cu alloy
CN117026055B (en) * 2023-10-09 2024-01-12 浙江金连接科技股份有限公司 Palladium alloy for semiconductor chip test probe and preparation method thereof

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JPS59107049A (en) * 1982-12-09 1984-06-21 Tanaka Kikinzoku Kogyo Kk Sliding contact material
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JP2011122194A (en) * 2009-12-09 2011-06-23 Tokuriki Honten Co Ltd Pd ALLOY FOR ELECTRIC-ELECTRONIC EQUIPMENT
WO2012077378A1 (en) * 2010-12-09 2012-06-14 株式会社徳力本店 Material for electrical/electronic use

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JPS59107049A (en) * 1982-12-09 1984-06-21 Tanaka Kikinzoku Kogyo Kk Sliding contact material
CN101809183A (en) * 2008-03-24 2010-08-18 株式会社久保田 Pipe provided with corrosion prevention layer on the outside surface, process for production of the same, and process for production of alloy wires to be used for corrosion prevention of outside surface of the pipe
JP2011122194A (en) * 2009-12-09 2011-06-23 Tokuriki Honten Co Ltd Pd ALLOY FOR ELECTRIC-ELECTRONIC EQUIPMENT
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Publication number Priority date Publication date Assignee Title
CN107075667A (en) * 2014-11-07 2017-08-18 住友金属矿山株式会社 Copper alloy target
CN107075667B (en) * 2014-11-07 2019-08-20 住友金属矿山株式会社 Copper alloy target
CN110317969A (en) * 2018-03-28 2019-10-11 住友金属矿山株式会社 The overlay film of solder bonding electrodes and solder bonding electrodes, which is formed, uses copper alloy target

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Publication number Publication date
US20150197834A1 (en) 2015-07-16
WO2014049874A1 (en) 2014-04-03
KR20150056556A (en) 2015-05-26
JPWO2014049874A1 (en) 2016-08-22
TW201422826A (en) 2014-06-16
TWI600773B (en) 2017-10-01
JP6142347B2 (en) 2017-06-07

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Application publication date: 20150603